This invention relates to electrophoretic media useful in the production of electrophoretic displays, to binders for use in such media, and to electrophoretic displays formed using such binders.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. It is shown in U.S. Pat. No. 7,170,670 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Electrophoretic displays have been the subject of intense research and development for a number of years. In a particle-based electrophoretic display, a plurality of charged particles move through a fluid under the influence of an electric field. Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
As noted above, electrophoretic media require the presence of a fluid. In most prior art electrophoretic media, this fluid is a liquid, but electrophoretic media can be produced using gaseous fluids; see, for example, Kitamura, T., et al., “Electrical toner movement for electronic paper-like display”, IDW Japan, 2001, Paper HCS1-1, and Yamaguchi, Y., et al., “Toner display using insulative particles charged triboelectrically”, IDW Japan, 2001, Paper AMD4-4). See also U.S. Pat. Nos. 7,321,459 and 7,236,291. Such gas-based electrophoretic media appear to be susceptible to the same types of problems due to particle settling as liquid-based electrophoretic media, when the media are used in an orientation which permits such settling, for example in a sign where the medium is disposed in a vertical plane. Indeed, particle settling appears to be a more serious problem in gas-based electrophoretic media than in liquid-based ones, since the lower viscosity of gaseous suspending fluids as compared with liquid ones allows more rapid settling of the electrophoretic particles.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT) and E Ink Corporation describe various technologies used in encapsulated electrophoretic and other electro-optic media. Such encapsulated media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles in a fluid medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. The technologies described in the these patents and applications include:                (a) Electrophoretic particles, fluids and fluid additives; see for example U.S. Pat. Nos. 7,002,728 and 7,679,814;        (b) Capsules, binders and encapsulation processes; see for example U.S. Pat. Nos. 5,930,026; 6,067,185; 6,130,774; 6,172,798; 6,249,271; 6,327,072; 6,392,785; 6,392,786; 6,459,418; 6,839,158; 6,866,760; 6,922,276; 6,958,848; 6,987,603; 7,061,663; 7,071,913; 7,079,305; 7,109,968; 7,110,164; 7,202,991; 7,242,513; 7,304,634; 7,339,715; 7,391,555; 7,411,719; 7,477,444; and 7,561,324; and U.S. Patent Applications Publication Nos. 2004/0112750; 2005/0156340; 2007/0057908; 2007/0091417; 2007/0223079; 2008/0023332; 2008/0130092; 2008/0264791; 2009/0122389; and 2010/0044894;        (c) Films and sub-assemblies containing electro-optic materials; see for example U.S. Pat. Nos. 6,982,178 and 7,839,564;        (d) Backplanes, adhesive layers and other auxiliary layers and methods used in displays; see for example U.S. Pat. Nos. 7,116,318; and 7,535,624;        (e) Color formation and color adjustment; see for example U.S. Pat. No. 7,075,502 and U.S. Patent Application Publication No. 2007/0109219;        (f) Methods for driving displays; see for example U.S. Pat. Nos. 7,012,600 and 7,453,445;        (g) Applications of displays; see for example U.S. Pat. No. 7,312,784 and U.S. Patent Application Publication No. 2006/0279527; and        (h) Non-electrophoretic displays, as described in U.S. Pat. Nos. 6,241,921; 6,950,220; and 7,420,549; and U.S. Patent Application Publication No. 2009/0046082.        
Many of the aforementioned patents and applications recognize that the walls surrounding the discrete microcapsules in an encapsulated electrophoretic medium could be replaced by a continuous phase, thus producing a so-called polymer-dispersed electrophoretic display, in which the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and that the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display may be regarded as capsules or microcapsules even though no discrete capsule membrane is associated with each individual droplet; see for example, the aforementioned U.S. Pat. No. 6,866,760. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic media are regarded as sub-species of encapsulated electrophoretic media.
A related type of electrophoretic display is a so-called “microcell electrophoretic display”. In a microcell electrophoretic display, the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film. See, for example, U.S. Pat. Nos. 6,672,921 and 6,788,449, both assigned to Sipix Imaging, Inc.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, the aforementioned U.S. Pat. Nos. 6,130,774 and 6,172,798, and U.S. Pat. Nos. 5,872,552; 6,144,361; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346. Other types of electro-optic displays may also be capable of operating in shutter mode.
An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; ink jet printing processes; electrophoretic deposition (See U.S. Pat. No. 7,339,715); and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
An electrophoretic display normally comprises a layer of electrophoretic material and at least two other layers disposed on opposed sides of the electrophoretic material, one of these two layers being an electrode layer. In most such displays both the layers are electrode layers, and one or both of the electrode layers are patterned to define the pixels of the display. For example, one electrode layer may be patterned into elongate row electrodes and the other into elongate column electrodes running at right angles to the row electrodes, the pixels being defined by the intersections of the row and column electrodes. Alternatively, and more commonly, one electrode layer has the form of a single continuous electrode and the other electrode layer is patterned into a matrix of pixel electrodes, each of which defines one pixel of the display. In another type of electrophoretic display, which is intended for use with a stylus, print head or similar movable electrode separate from the display, only one of the layers adjacent the electrophoretic layer comprises an electrode, the layer on the opposed side of the electrophoretic layer typically being a protective layer intended to prevent the movable electrode damaging the electrophoretic layer.
The manufacture of a three-layer electrophoretic display normally involves at least one lamination operation. For example, in several of the aforementioned MIT and E Ink patents and applications, there is described a process for manufacturing an encapsulated electrophoretic display in which an encapsulated electrophoretic medium comprising capsules in a binder is coated on to a flexible substrate comprising indium-tin-oxide (ITO) or a similar conductive coating (which acts as one electrode of the final display) on a plastic film, the capsules/binder coating being dried to form a coherent layer of the electrophoretic medium firmly adhered to the substrate. Separately, a backplane, containing an array of pixel electrodes and an appropriate arrangement of conductors to connect the pixel electrodes to drive circuitry, is prepared. To form the final display, the substrate having the capsule/binder layer thereon is laminated to the backplane using a lamination adhesive. (A very similar process can be used to prepare an electrophoretic display usable with a stylus or similar movable electrode by replacing the backplane with a simple protective layer, such as a plastic film, over which the stylus or other movable electrode can slide.) In one preferred form of such a process, the backplane is itself flexible and is prepared by printing the pixel electrodes and conductors on a plastic film or other flexible substrate. The obvious lamination technique for mass production of displays by this process is roll lamination using a lamination adhesive. Similar manufacturing techniques can be used with other types of displays. For example, a microcell electrophoretic medium may be laminated to a backplane in substantially the same manner as an encapsulated electrophoretic medium.
As discussed in the aforementioned U.S. Pat. No. 6,982,178, (see column 3, lines 63 to column 5, line 46) many of the components used in electrophoretic displays, and the methods used to manufacture such displays, are derived from technology used in liquid crystal displays (LCD's), which are of course also electro-optic displays, though using a liquid rather than a solid medium. For example, electrophoretic displays may make use of an active matrix backplane comprising an array of transistors or diodes and a corresponding array of pixel electrodes, and a “continuous” front electrode (in the sense of an electrode which extends over multiple pixels and typically the whole display) on a transparent substrate, these components being essentially the same as in LCD's. However, the methods used for assembling LCD's cannot be used with electrophoretic displays. LCD's are normally assembled by forming the backplane and front electrode on separate glass substrates, then adhesively securing these components together leaving a small aperture between them, placing the resultant assembly under vacuum, and immersing the assembly in a bath of the liquid crystal, so that the liquid crystal flows through the aperture between the backplane and the front electrode. Finally, with the liquid crystal in place, the aperture is sealed to provide the final display.
This LCD assembly process cannot readily be transferred to electrophoretic displays. Because the electrophoretic material is solid, it must be present between the backplane and the front electrode before these two integers are secured to each other. Furthermore, in contrast to a liquid crystal material, which is simply placed between the front electrode and the backplane without being attached to either, an electrophoretic medium normally needs to be secured to both; in most cases the electrophoretic layer is formed on the front electrode, since this is generally easier than forming this layer on the circuitry-containing backplane, and the front electrode/electrophoretic layer combination is then laminated to the backplane, typically by covering the entire surface of the electrophoretic layer with an adhesive and laminating under heat, pressure and possibly vacuum. Accordingly, most prior art methods for final lamination of electrophoretic displays are essentially batch methods in which (typically) the electrophoretic medium, a lamination adhesive and a backplane are brought together immediately prior to final assembly, and it is desirable to provide methods better adapted for mass production.
Electro-optic displays are often costly; for example, the cost of the color LCD found in a portable computer is typically a substantial fraction of the entire cost of the computer. As the use of electro-optic displays spreads to devices, such as cellular telephones and personal digital assistants (PDA's), much less costly than portable computers, there is great pressure to reduce the costs of such displays. The ability to form layers of some solid electro-optic media by printing techniques on flexible substrates, as discussed above, opens up the possibility of reducing the cost of electro-optic components of displays by using mass production techniques such as roll-to-roll coating using commercial equipment used for the production of coated papers, polymeric films and similar media.
The aforementioned U.S. Pat. No. 6,982,178 describes a method of assembling a solid electro-optic display (including an electrophoretic display) which is well adapted for mass production. Essentially, this patent describes a so-called “front plane laminate” (“FPL”) which comprises, in order, a light-transmissive electrically-conductive layer; a layer of a solid electro-optic medium in electrical contact with the electrically-conductive layer; an adhesive layer; and a release sheet. Typically, the light-transmissive electrically-conductive layer will be carried on a light-transmissive substrate, which is preferably flexible, in the sense that the substrate can be manually wrapped around a drum (say) 10 inches (254 mm) in diameter without permanent deformation. The term “light-transmissive” is used in this patent and herein to mean that the layer thus designated transmits sufficient light to enable an observer, looking through that layer, to observe the change in display states of the electro-optic medium, which will normally be viewed through the electrically-conductive layer and adjacent substrate (if present); in cases where the electro-optic medium displays a change in reflectivity at non-visible wavelengths, the term “light-transmissive” should of course be interpreted to refer to transmission of the relevant non-visible wavelengths. The substrate will typically be a polymeric film, and will normally have a thickness in the range of about 1 to about 25 mil (25 to 634 μm), preferably about 2 to about 10 mil (51 to 254 μm). The electrically-conductive layer is conveniently a thin metal or metal oxide layer of, for example, aluminum or ITO, or may be a conductive polymer. Poly(ethylene terephthalate) (PET) films coated with aluminum or ITO are available commercially, for example as “aluminized Mylar” (“Mylar” is a Registered Trade Mark) from E.I. du Pont de Nemours & Company, Wilmington Del., and such commercial materials may be used with good results in the front plane laminate.
The aforementioned U.S. Pat. No. 6,982,178 also describes a method for testing the electro-optic medium in a front plane laminate prior to incorporation of the front plane laminate into a display. In this testing method, the release sheet is provided with an electrically conductive layer, and a voltage sufficient to change the optical state of the electro-optic medium is applied between this electrically conductive layer and the electrically conductive layer on the opposed side of the electro-optic medium. Observation of the electro-optic medium will then reveal any faults in the medium, thus avoiding laminating faulty electro-optic medium into a display, with the resultant cost of scrapping the entire display, not merely the faulty front plane laminate.
The aforementioned U.S. Pat. No. 6,982,178 also describes a second method for testing the electro-optic medium in a front plane laminate by placing an electrostatic charge on the release sheet, thus forming an image on the electro-optic medium. This image is then observed in the same way as before to detect any faults in the electro-optic medium.
Assembly of an electro-optic display using such a front plane laminate may be effected by removing the release sheet from the front plane laminate and contacting the adhesive layer with the backplane under conditions effective to cause the adhesive layer to adhere to the backplane, thereby securing the adhesive layer, layer of electro-optic medium and electrically-conductive layer to the backplane. This process is well-adapted to mass production since the front plane laminate may be mass produced, typically using roll-to-roll coating techniques, and then cut into pieces of any size needed for use with specific backplanes.
The aforementioned U.S. Pat. No. 7,561,324 describes a so-called “double release sheet” which is essentially a simplified version of the front plane laminate of the aforementioned U.S. Pat. No. 6,982,178. One form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two adhesive layers, one or both of the adhesive layers being covered by a release sheet. Another form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two release sheets. Both forms of the double release film are intended for use in a process generally similar to the process for assembling an electro-optic display from a front plane laminate already described, but involving two separate laminations; typically, in a first lamination the double release sheet is laminated to a front electrode to form a front sub-assembly, and then in a second lamination the front sub-assembly is laminated to a backplane to form the final display, although the order of these two laminations could be reversed if desired.
U.S. Pat. No. 7,839,564 describes a so-called “inverted front plane laminate”, which is a variant of the front plane laminate described in the aforementioned U.S. Pat. No. 6,982,178. This inverted front plane laminate comprises, in order, at least one of a light-transmissive protective layer and a light-transmissive electrically-conductive layer; an adhesive layer; a layer of a solid electro-optic medium; and a release sheet. This inverted front plane laminate is used to form an electro-optic display having a layer of lamination adhesive between the electro-optic layer and the front electrode or front substrate; a second, typically thin layer of adhesive may or may not be present between the electro-optic layer and a backplane. Such electro-optic displays can combine good resolution with good low temperature performance.
It will readily be apparent from the foregoing discussion that an electrophoretic display is a complicated system, which may comprise (1) the electrophoretic particles themselves, which may be complex particles having a core/shell construction and/or a polymer coating; (2) the fluid surrounding the electrophoretic particles; (3) additives in this fluid, such as charge control agents, surfactants, dispersed polymers etc; (4) a capsule wall surrounding the electrophoretic particles and fluid; a binder or other continuous phase surrounding the capsules, droplets or microcells; (5) one or more adhesive layers; and (6) one or more electrode layers. Not surprisingly, in view of the complexity of this system, the exact relationship between the electro-optic properties of such a display and the mechanical, physic-chemical and electrical properties of the various materials used to form the display is only partially understood. It is for example, known that if the adhesive used in a front plane laminate has insufficient electrical conductivity, the electro-optic performance of the display may be adversely affected. The aforementioned U.S. Pat. No. 7,012,735 describes the advantage obtained by doping this adhesive with salts or other materials to improve its electrical conductivity, a preferred dopant for this purpose being tetrabutylammonium hexafluorophosphate (hereinafter “TBAHFP”). The same patent also describes the advantages of similar doping of the binder of the display with salts, including such as TBAHFP.
One of the problems that doping of the binder is designed to reduce or overcome is so-called “white state degradation” or “WSD”. WSD manifests itself as a reduction of the reflectivity (typically measured as L* value in the usual CIE L*a*b* color space) of the white extreme optical state of the display during operation of the display. It has been found empirically that the amount of WSD experienced is dependent upon operating duty cycle, temperature and composition of the internal phase (electrophoretic particles plus fluid) of the electrophoretic medium. Certain electrophoretic media of the type described in U.S. Patent Application Publication No. 2010/0289736, and lacking ionic dopant in the binder, have been found to experience WSD of 2-9 L* units in the first 48 hours of operation at a 20 per cent duty cycle at 25° C. This degree of WSD is unacceptable for many applications, which require WSD not greater than about 3 L* units (and desirably considerably less) after 240 hours of operation under these conditions.
Although the addition of an ionic dopant, typically a salt, to the binder reduces WSD, the choice of an appropriate salt poses considerable difficulties. In practice, the fluids used in the internal phases of electrophoretic displays are organic materials, typically low molecular weight hydrocarbons, and the binders are polymers formed from aqueous solutions or dispersions, the most common type of binder being a polyurethane added in the form of an aqueous latex. The latex is mixed with the capsules (when such capsules are present), or the internal phase is emulsified in the latex (in the case of a polymer-dispersed electrophoretic medium). The slurry formed by the latex and the capsules or droplets is then coated on to a substrate, and the layer of slurry dried to form a coherent electrophoretic layer. At first glance it might appear that the ionic dopant should be a water-soluble salt, which can readily be added to the aqueous polymer latex in the form of an aqueous solution. However, it is found that simple, water-soluble salts such as sodium chloride are not effective in mitigating WSD; for example, addition of a molar amount of sodium chloride equivalent to 250-350 ppm of TBAHPF to the binder of an electrophoretic medium of the type described in the aforementioned 2010/0289736 gave a WSD of about 7.5 L* units after 240 hours of operation at a 20 per cent duty cycle at 25° C. Better results are achieved with some hydrophobic (water insoluble) salts; for example addition of 250-350 ppm of the TBAHFP mentioned in U.S. Pat. No. 7,012,735 gives a WSD of about 1 L* unit under the same conditions. The impact of these salts on WSD is concentration dependent, and their impact on the broader range of EO performance (including for example this film transistor (TFT) performance, image stability, and dwell state dependence) is sensitive to the concentration of other components in the slurry. Other components that apparently interact with slurry dopant to affect EO performance include Triton X100 and the solvent used to deliver the salt into solution.
Unfortunately, such water insoluble salts pose other problems. It is essential that the salt be uniformly dispersed throughout the binder, and simply dispersing the salt in water will not suffice to produce such uniform dispersion. In practice, it is necessary to dissolve the salt in an appropriate water-miscible organic solvent and add the solution of the salt in the solvent to the latex from which the binder is formed. The solvent chosen must not, of course, have any adverse effect on the capsules or droplets, the binder itself or the properties of the final dried electrophoretic layer. Appropriate solvents are in practice limited to N-methylpyrrolidone (NMP), tetrahydrofuran and acetone. It is difficult to remove all traces of the organic solvent from the electrophoretic layer during drying, since the drying conditions are limited to conditions which can be tolerated by the capsules or droplets, which contain a volatile organic fluid. Traces of organic solvents remaining in the dried electrophoretic layer or adhesive layer are known to cause serious problems; see, for example, the aforementioned 2009/0122389, which describes damage to backplanes containing organic semiconductors caused by traces of NMP remaining in the dried adhesive layer. It has also been found that traces of organic solvents remaining in the dried binder can have negative impacts on the electro-optic performance on the display; for example, such organic solvents has adversely affect white state edge, and the darkness of the dark state of the display.
Accordingly, there is a need for a method of adding ionic dopants to binders used in electrophoretic media without introducing organic solvents into the binders, and the present invention provides such a method.